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Activation of carbon monoxide and carbon dioxide by transition metal carbonyl complexes

Thesis/Dissertation ·
OSTI ID:6188518

The development of new carbon resources to be used either as fuels or as chemical feedstocks has been of major concern to the industrial community since the oil shortage in the early 1970s. The first study involved the binding of CO2 to a variety of transition metal carbonyl anions. It was found that the nucleophilicity of the metal center greatly affected the coordination of CO2. This work then was extended into an investigation of the low pressure reduction of CO2 to methyl formate by a rhenium carbonyl catalyst. Infrared spectroscopy was used to characterize the active species and probe the mechanism of the reaction. It was found that this rhenium carbonyl system was more effective towards the reduction of CO than CO2. The second study dealt with the conversion of synthesis gas and HCl (g) to methyl chloride under mild temperatures and pressures by a supported iridium carbonyl catalyst. Several different routes to methyl chloride were identified within the system. IR spectroscopy was used to identify the active species in the reaction and investigate their various modes of deactivation. It was shown that discrete iridium carbonyl complexes existed under the employed reaction conditions. Finally, a mechanism for the formation of methyl chloride in this system was proposed. This study concluded with an examination of other supported metal carbonyl catalysts. It was found that a change in the composition of the metal catalyst could alter the activity and selectivity of the reaction. In this respect, a supported ruthenium carbonyl catalyst was observed to be active towards the formation of ethyl chloride and various other two-carbon products.

Research Organization:
Florida Univ., Gainesville (USA)
OSTI ID:
6188518
Country of Publication:
United States
Language:
English